Furfuraldehyde-acetonyl acetone reaction product and method



Patented July 25, 1950 REACTIONv PRODUCT AND METHOD Mortimer '1. Harvey,South Orange, N. J., and

SolbmorrCaplan, New York, N. Y., assignors to Harvel' ResearchCorporation, a corporation of New Jersey No Drawing. ApplicatiomMay 26,1949, Serial No. 95,568

This invention relates to novel'org anic condensationreaction productsand to methods for'preparing the same. In its more specificaspect theinvention is directed toresinous organic condensation reaction productsof acetonyl acetone and furfuraldehyde and tomethods for preparing thesame. The present application is a continuation in part of our copendingapplication Ser. No. 560,358, filed October 25, 1944, now abandoned,which in turn is a continuation-in-part of our application Ser. No.461,202 filed October '7, 1942, now Patent Number 2,363,829.

In the course of our experimentations with furfuraldehyde we havediscovered that furfuraldehyde may be-reactedwith acetonyl acetone underalkaline conditions. to produce novel resinous condensation reactionproducts which are insoluble in water, have high boiling points, may beemployed as plasticizers for solid resins such as polyvinyl chloride,polyvinylacetate, copolymers of vinyl chloride and vinyl acetate and thelike. They may also be reacted with an aldehyde such asformaldehyde.under acidic conditions to produce thermosetting resins; they may bepolymerized under acid conditions and they may be employed incombination with the well known phenol-formaldehyde resins to imparthigh alkali resistance thereto.

According to this invention acetonyl acetone (hexandione 2,5). is.reactedwith furfuraldehyde under alkaline conditions to produce resinousproducts capable of being reacted under acidic conditions withformaldehyde. to form thermosetting resins. In the practice of theinvention there is formed a mixture of acetonyl acetone andfurfuraldehyde. The pH ofv this mixture is adjusted by the addition ofany suitable. alkali such as sodium hydroxide, potassium hydroxide orthe like in such proportion that the pH of the mixture is raised above 7and preferably between about 8.5 and 14. While the ratio by moles of theacetonyl acetone to the furfuraldehyde in said mixture may vary overwide limits, for plant operation it is preferable that it be betweenabout 1 to 1 and 1 to 8, and for most purposes 1 to 3, to 1 to 8. Wehave discovered that by varying the mole ratio as above set forth, thatunder a given procedure we may produce resinous organic condensationreaction products varying from hard brittle masses to readily pourableliquids each of which is capable of reacting with formaldehyde underacidic conditions for the production of thermosetting resins. In thegeneral practice of this invention we prefer to employ a mixture offurfuraldehyde, acetonyl acetone and alkali in 3 Claims. (Cl--260-64)sufiicientquantityso that the pH. of: the mixture is between 8:5 and14'. This so adjusted mixture may be placed under a reflux condenser. Wehave found that upon the. addition of the alkali to the furfuraldehydeand acetonyl acetone mixture, an exothermic reaction setsinsubstantially immediately. This. exothermic reaction is allowed tocontinue and after it has subsided We prefer to-heat. the massto boilingandlwe prefer to maintain it in thiszstateof boiling under said refluxcondenser in order to. assure completeness of reaction and to assuregood yields of. resinous material which. measures at least 25%. of theorganicv reaction. mass and. has a viscosityv of at least 1000centi'poises at 25 C.

The invention accordingly comprises the several steps and the relationof. one or more of such steps with. respect to. each of the. others, andcompositions of matter produced thereby, all ofwhich will.beexemplifiedfin the following detailed disclosure, and. the scope ofthev invention will be indicated in the claims.

For a fuller understanding of the invention, referenceshould be had tothe following examples which are given toillustr-ate further theinvention and. arenot to. be: construed in a limiting sense, all partsbeing. given by: weight, unless otherwise indicated.

Example 1.--1' mole of furfuraldehyde, 1 mole'of. acetonyl acetone 96'.grams. of furfuraldehyde, 1-14. gramsloface tonyl acetone and: asolutionof. one gram: of: sodium hydroxide in 2'; grams: of water were mixedtogether and placed. under a reflux condenser. An. extremely vigorous.exothermic: reaction set. in immediately afterthe additionofthesodium-hydroxide. After the exothermic reaction had subsided heat wasthen applied and the mass was kept at refluxing or boiling temperaturefor one hour resulting in the production of an extremely viscousresinous mass which is one of the novel reaction products of thisinvention. This extremely viscous resinous mass may then be neutralizedwith dilute sulphuric acid. This resinous viscous mass may be heated oneither the acid or alkaline side to convert it to the solid state. Italso may be reacted with formaldehyde in the following manner: grams of37 /2% aqueous formaldehyde solution and 4 grams of lactic acid (80%)were added to said viscous mass and the reaction mixture was heatedunder a reflux condenser at refluxing temperature for 45 minutes. Theupper, aqueous layer was then poured off, leaving a plastic or resinousmass that was almost solid but fusible, A sample of this plasticresinous mass gelled in minutes when heated in an oven at 120 C.

Example 2.1 mole furjaraldehyde, A mole of acetonyl acetone 96 grams offurfuraldehyde, 28'grams of acetonyl acetone and a solution of 1 gram ofsodium hydroxide in 2 grams of water were mixed together and placedunder a reflux condenser. A vigorous exothermic reaction took place.After the exothermic action had subsided, heat was applied and thereaction mass was heated at refluxing or boiling temperature for onehour to provide a liquid resinous product which was then neutralizedwith dilute sulphuric acid. The soneutralized novel liquid resinousreaction product may be reacted with an aldehyde such as formaldehyde inthe following manner: 80 grams of 37 /2% aqueous formaldehyde solutionand 4 grams of lactic acid (80%) were added and the mixture heated undera reflux condenser at refluxing temperature for 2 hours. An extremelyviscous mass was formed from which the upper aqueous layer was easilydecanted. The remaining mass was a fusible resin. A sample of thisresin, without dehydration, gelled when placed in an oven for 20 minutesat 120 C.

Example 3.1 mole jurfumldehyde, V mole of acetonyl acetone 96 grams ofiuriuraldehyde, 14 grams of acetonyl acetone and a solutionof 1 gram ofsodium hydroxide in 2 grams of water were mixed together and heatedunder a reflux condenser at refluxing or boiling temperature for 1 hour.The resultant novel liquid resinous reaction product was thenneutralized with dilute sulphuric acid and 80 grams of 37V aqueousformaldehyde solution and 4 grams of lactic acid (80%) were addedthereto. The mixture was heated under a reflux condenser at refluxingtemperature for 2 hours at the end of which time the mixture gelled.

Example 4.1 mole of furfuraldehyde, $4; mole of acetonyl acetone 96grams of furfuraldehyde, 14 grams of acetonyl acetone and a solution of1 gram of sodium hydroxide in 2 grams of water were heated togetherunder a reflux condenser at refluxing or boiling temperature for 1 hourand then the resultant novel liquid resinous reaction product wasneutralized with dilute sulphuric acid after which grams of 37 aqueousformaldehyde solution and /2 gram of lactic acid (80%) were added andthe mixture was heated under a reflux condenser at refluxing temperatureof 1 hours. An upper aqueous layer was decanted off leaving 4 the lowerlayer of fusible resin. A sample of this resin gelled in 30 minutes whenheated in an oven at G.

Since certain changes in carrying out the above process and certainmodifications in the compositions which embody the inventionmay be madewithout departing from its scope, it is intended that all mattercontained in the above description shall be interpreted as illustrativeand not in a limiting sense.

It is also to be understood that the following claims are intended tocover all the generic and specific features of the invention hereindescribed and all statements of the scope of the invention, which as amatter of language might be said to fall therebetween; and that they areintended to be inclusive in scope and not exclusive, in that, ifdesired, other materials may be added to the novel composition of matterherein claimed without departing from the spirit of the invention.Particularly'it is to be understood that in said claims, ingredients orcomponents recited in the singular are intended to include compatiblemixtures of said ingredients wherever the sense permits.

Having described our invention, what we claim and desire to protect byLetters Patent is:

1. The method for producinga resinous product whose viscosity is atleast 1000 centipoises at 25 C. comprising reacting furfuraldehyde andacetonyl acetone under alkaline conditions and heating the resultantmass until said resin is produced in an amount equal to at least 25% ofthe organic reaction mass.

2. The method forproduoin'g a resinous product whose viscosity is atleast 1000 centipoises at 25 C. comprising reacting furfuraldehyde andacetonyl acetone under alkaline conditions, the mole ratio of saidfurfuraldehyde to said acetonyl acetone being in the range of 1-1 to8-1, and under said alkaline. conditions heating said reaction massuntil said resin is produced.

13. A resino'us product made according to claim 1. v

' ,MORTIMER T. HARVEY.

SOLOMON CAPLAN.

' REFERENCES CITED Thefollowing referencesare of record in the file ofthis patent:

UNITED STATES PATENTS Beilstein Handbuch d. Organische Chemie, vol. 1,4th ed., page 789. V

1. THE METHOD FOR PRODUCING A RESINOUS PRODUCT WHOSE VISOCITY IS ATLEAST 1000 CENTIPOISES AT 25*C. COMPRISING REACTING FURFURALDEHYDE ANDACETONYL ACETONE UNDER ALKALINE CONDITIONS AND HEATING THE RESULTANTMASS UNTIL SAID RESIN IS PRODUCED IN AN AMOUNT EQUAL TO AT LEAST 25% OFTHE ORGANIC REACTION MASS.